Cross-linkable polymers and electronic devices made with such polymers

ABSTRACT

The present invention relates to novel cross-linkable polymers and a wide variety of electronic devices containing at least one layer having the polymer. The compounds can function as monomers, and copolymers can be formed from such monomers, such copolymers comprising, as polymerized units, a plurality of units of the compounds.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel compounds useful as holetransport materials in making electronic devices. The invention furtherrelates to electronic devices having at least one active layercomprising such a hole transport material.

2. Background

In organic photoactive electronic devices, such as organic lightemitting diodes (“OLED”), that make up OLED displays, the organic activelayer is sandwiched between two electrical contact layers in an OLEDdisplay. In an OLED the organic photoactive layer emits light throughthe light-transmitting electrical contact layer upon application of avoltage across the electrical contact layers.

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules,conjugated polymers, and organometallic complexes have been used.

Devices that use photoactive materials frequently include one or morecharge transport layers, which are positioned between a photoactive(e.g., light-emitting) layer and a contact layer (hole-injecting contactlayer). A device can contain two or more contact layers. A holetransport layer can be positioned between the photoactive layer and thehole-injecting contact layer. The hole-injecting contact layer may alsobe called the anode. An electron transport layer can be positionedbetween the photoactive layer and the electron-injecting contact layer.The electron-injecting contact layer may also be called the cathode.

Production of electronic devices, including photo-active devices, relieson certain properties in materials used in the devices, includingfilm-forming ability, solubility, and thermal stability. Moreover, it isoften desirable that materials have reduced solubility when they areused in forming multiple layers in a device.

There is a continuing need for charge transport materials for use inelectronic devices.

SUMMARY OF THE INVENTION

The compounds disclosed herein are useful in making charge transportlayers for use in electronic devices. The charge transport layers can beused in any application wherein charge transport capacity is desired.Examples of some uses include, but are not limited to, organiclight-emitting diodes (“OLED”s), photovoltaic cells, light sensors, thinfilm organic transistors, photoconductors, and electrophotographicapplications.

Examples of other organic electronic devices that may benefit formhaving one or more layers comprising the new compounds and compositionsdescribed herein include: (1) devices that convert electrical energyinto radiation (e.g., a light-emitting diode, light emitting diodedisplay, or diode laser), (2) devices that detect signals throughelectronics processes (e.g., photodetectors (e.g., photoconductivecells, phototoresistors, phototswitches, photototransistors,phototubes), IR detectors, (3) devices that convert radiation inotelectrical energy, (e.g., a photovoltaic device or solar cell), and (4)devices that include one or more electronic components that include oneor more organic semi-conductor layers (e.g., a transistor or diode).

The compositions and methods disclosed herein allow the reduction ofsolubility of a compound for use in an electronic device afterdeposition of the material to form a layer in the device. The compoundsdisclosed herein are crosslinkable, i.e., crosslinking can be induced inthe compounds due to the incorporation within the compounds ofcrosslinkable groups.

Examples of crosslinkable groups include substituted vinyl groups,acrylate groups (e.g. ethenyl (CH₂═CH—)), propenyl ((CH₃)(H)C═CH—),acryloyl (CH₂═CH—C(O)—O—), and methacryloyl (CH₂═C(CH₃)—C(O)—O—), cyclicethers and siloxanes. In addition, a crosslinkable or “crosslinking”group can be any organic fragment that can bind to a preformed support,and that can be further polymerized after it is bound to the support.Generally, any polymerizable group can function as a crosslinkablegroup. Any organic or inorganic material can be used as a support aslong as it meets desired solubility properties, and has reactive sitesthat can covalently link a compound to the surface thereof. Suchmaterials are well known and include polystyrene, polyalcohols,polyacrylates, polysilanes and polysiloxanes.

One aspect of the present invention is a compound having the formula(I):

wherein

-   -   n is an integer of at least 1 and R¹ is selected from aryl,        heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1        or more fluorine atoms, for example, up to 7 fluorine atoms, and        a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        and fluoroheteroaryl substituted with 1 or more fluorine atoms,        for example, up to 7 fluorine atoms. The compound comprises more        than one group R¹, and R¹ can be different at each occurrence.        For example, the compound represented by formula (I) can        function as a monomer, and copolymers can be formed from the        compound, such copolymers comprising, as polymerized units, a        plurality of units having formula (I) in which at least one unit        contains R¹ different from R¹ in other units. In some        embodiments, R¹ is aryl.

R³ is selected from H and R¹. R² is selected from H, aryl, alkyl,fluoroalkyl, Cl, Br, I, heteroaryl, fluoroaryl, and fluoroheteroarylsubstituted with 1 or more fluorine atoms, for example, up to 7 fluorineatoms, a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,fluoroheteroaryl substituted with 1 or more fluorine atoms, for example,up to 7 fluorine atoms a crosslinkable group, and an arylamino group offormula (11),

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl. In someembodiments R⁴ is aryl. R⁷ is selected from aryl, heteroaryl,fluoroaryl, fluoroheteroaryl substituted with 1 or more fluorine atoms,for example, up to 7 fluorine atoms, and a crosslinkable group attachedto aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1or more fluorine atoms, for example up to 7 fluorine atoms.

In some embodiments, R² is H. In some embodiments, R² is different fromR³. In some embodiments, R² is H and R³ is aryl. In some embodiments,when R¹ or R³ are directly bound to a nitrogen atom, the crosslinkablegroup is not a vinyl group.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,and E is (CR⁵R⁶)_(m), such that when n is greater than 1 and m is 1, atleast one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) has one or more substituents independently selected from H,F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy,fluoroaryloxy, and crosslinkable groups. In further embodiments,substituents on two neighboring aromatic rings in the compound offormula (I) can together form an aromatic or non-aromatic ring.Neighboring aromatic rings can be adjacent or vicinal. In furtherembodiments, adjacent substituents on a single ring can be linked toform a fused aromatic or non-aromatic ring.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, R¹ is selected from cinnamate andchalcone groups. In some embodiments, n=1, R² is H, and R³ is selectedfrom phenyl, 1-naphthyl and 2-naphthyl.

Another aspect of the invention is a composition comprising a compoundhaving formula (I) as defined hereinabove.

Another aspect of the present invention is a compound of formula

wherein

-   -   n is an integer of at least 1, R¹ is selected from aryl,        heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1        or more fluorine atoms, for example, up to 7 fluorine atoms, and        a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        and fluoroheteroaryl substituted with 1 or more fluorine atoms,        for example, up to 7 fluorine atoms. R¹ may be different at each        occurrence (i.e. copolymers). R² is selected from H, aryl,        alkyl, fluoroalkyl, Cl, Br, I, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, a crosslinkable group attached        to aryl, heteroaryl, fluoroaryl, fluoroheteroaryl substituted        with 1 or more fluorine atoms, for example, up to 7 fluorine        atoms, a crosslinkable group, and arylamino of formula (II). In        some embodiments, when R¹ or R³ are directly bound to a nitrogen        atom, the crosslinkable group is not a vinyl group. In some        embodiments, R² is H or aryl. R⁴ is selected from aryl, H, R¹,        alkyl, fluoroalkyl. In some embodiments R⁴ is aryl. R⁷ is        selected from aryl, heteroaryl, fluoroaryl, fluoroheteroaryl        substituted with 1 or more fluorine atoms, for example up to 7        fluorine atoms and a crosslinkable group attached to aryl,        heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1        or more fluorine atoms, for example up to 7 fluorine atoms.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (III) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, and acrosslinkable group. In further embodiments, substituents on twoneighboring aromatic rings in the compound of formula (III) can togetherform an aromatic or non-aromatic ring. In further embodiments, adjacentsubstituents on a single ring can be linked to form a fused aromatic ornon-aromatic ring.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, n=1, and R² is arylamino of formula(II), wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl.In some embodiments, n=1, R¹ is selected from phenyl, 1-naphthyl or2-naphthyl and R² is a cinnamyl group. In some embodiments, n=1, R¹ isselected from phenyl, 1-naphthyl or 2-naphthyl and R² is arylamino offormula (II), wherein R⁴ is selected from aryl, H, or cinnamate. In someembodiments, R¹ is selected from phenyl, 1-naphthyl or 2-naphthyl and R²is selected from H or aryl and E is selected from (CR⁵R⁶)_(m), whereinR⁵ is selected from alkyl, aryl, alkoxy and R⁶ is a crosslinkable group.

Another aspect of the present invention is a composition comprising acompound of formula (III) as defined hereinabove.

Another aspect of the present invention is a compound of formula

wherein:

-   -   R¹ is selected from aryl, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, and a crosslinkable group        attached to aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl        substituted with 1 or more fluorine atoms, for example, up to 7        fluorine atoms, and may be different at each occurrence (i.e.        copolymers). In some embodiments, R¹ is aryl. R² is selected        from H, aryl, alkyl, fluoroalkyl, Cl, Br, I, heteroaryl,        fluoroaryl, and fluoroheteroaryl substituted with 1 or more        fluorine atoms, for example, up to 7 fluorine atoms, a        crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, a crosslinkable group, and        arylamino of formula (II). In some embodiments, when R¹ or R³        are directly bound to a nitrogen atom, the crosslinkable group        is not a vinyl group. In some embodiments, R² is H or aryl. R⁴        is selected from aryl, H, R¹, alkyl, fluoroalkyl. In some        embodiments R⁴ is aryl. R⁷ is selected from aryl, heteroaryl,        fluoroaryl, fluoroheteroaryl substituted with 1 or more fluorine        atoms, for example up to 7 fluorine atoms and a crosslinkable        group attached to aryl, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example up to 7 fluorine atoms.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy and acrosslinkable group. In some embodiments, R¹ is selected from phenyl,1-naphthyl, and 2-naphthyl. In some embodiments, n=1, R² is H, and R³ isselected from phenyl, 1-naphthyl and 2-naphthyl. In some embodiments,n=1, R¹ is selected from phenyl, 1-naphthyl and 2-naphthyl and R² is acinnamyl group.

Another aspect of the invention is a composition comprising a compoundhaving formula (IV) as defined hereinabove.

Another aspect of the present invention is a composition comprisingcopolymers prepared by copolymerizing at least one functional monomerhaving the formula (I) or (III) as defined hereinabove with at least onecrosslinkable group as defined above. The polymerization can beperformed using thermal or photochemical polymerization methods.

The crosslinking can take place during or after polymerization. In oneembodiment, R² is a photosensitive or thermally sensitive group andcrosslinking can be initiated after polymerization of one or moremonomers of formula (I). Polymers having these groups can be formed intofilms, and then treated with heat or actinic radiation to crosslink.Crosslinked films are generally more robust and resistant to solventsthat may be used in later processing steps. Crosslinking groups are wellknown, and any can be used so long as they do not detrimentally affectthe desired properties of the polymer.

Another embodiment is an electronic device having at least one layercomprising a composition having the formula:

wherein

-   -   n is an integer of at least 1 and R¹ is selected from aryl,        heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1        or more fluorine atoms, for example, up to 7 fluorine atoms, and        a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        and fluoroheteroaryl substituted with 1 or more fluorine atoms,        for example, up to 7 fluorine atoms. The compound comprises more        than one group R¹, and R¹ can be different at each occurrence.        For example, the compound represented by formula (I) can        function as a monomer, and copolymers can be formed from the        compound, such copolymers comprising, as polymerized units, a        plurality of units having formula (I) in which at least one unit        contains R¹ different from R¹ in other units. In some        embodiments, R¹ is aryl.

R³ is selected from H and R¹. R² is selected from H, aryl, alkyl,fluoroalkyl, Cl, Br, I, heteroaryl, fluoroaryl, and fluoroheteroarylsubstituted with 1 or more fluorine atoms, for example, up to 7 fluorineatoms, a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,fluoroheteroaryl substituted with 1 or more fluorine atoms, for example,up to 7 fluorine atoms, a crosslinkable group, and an arylamino group offormula (II)

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl. In someembodiments R⁴ is aryl. R⁷ is selected from aryl, heteroaryl,fluoroaryl, fluoroheteroaryl substituted with 1 or more fluorine atoms,for example, up to 7 fluorine atoms, and a crosslinkable group attachedto aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1or more fluorine atoms, for example up to 7 fluorine atoms. In someembodiments, when R¹ or R³ are directly bound to a nitrogen atom, thecrosslinkable group is not a vinyl group.

In some embodiments, R² is H. In some embodiments, R² is different fromR³. In some embodiments, R² is H and R³ is aryl.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,and E is (CR⁵R⁶)_(m), such that when n is greater than 1 and m is 1, atleast one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) has one or more substituents independently selected from H,F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy,fluoroaryloxy, and crosslinkable groups. In further embodiments,substituents on two neighboring aromatic rings in the compound offormula (I) can together form an aromatic or non-aromatic ring.Neighboring aromatic rings can be adjacent or vicinal. In furtherembodiments, adjacent substituents on a single ring can be linked toform a fused aromatic or non-aromatic ring.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, R¹ is selected from cinnamate andchalcone groups. In some embodiments, n=1, R² is H, and R³is selectedfrom phenyl, 1-naphthyl and 2-naphthyl.

In some embodiments, the device is selected from a light-emitting diode,a light-emitting diode display, a laser diode, a photodetector,photoconductive cell, photoresistor, photoswitch, phototransistor,phototube, IR-detector, photovoltaic device, solar cell, light sensor,photoconductor, electrophotographic device, transistor, and a diode.

Another aspect of the present invention is an electronic device havingat least one layer comprising a composition comprising a compound offormula

wherein

-   -   n is an integer of at least 1, R¹ is selected from aryl,        heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1        or more fluorine atoms, for example, up to 7 fluorine atoms, and        a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        and fluoroheteroaryl substituted with 1 or more fluorine atoms,        for example, up to 7 fluorine atoms. R¹ may be different at each        occurrence (i.e. copolymers). R² is selected from H, aryl,        alkyl, fluoroalkyl, Cl, Br, I, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, a crosslinkable group attached        to aryl, heteroaryl, fluoroaryl, fluoroheteroaryl substituted        with 1 or more fluorine atoms, for example, up to 7 fluorine        atoms, a crosslinkable group, and arylamino of formula (II). In        some embodiments, R² is H or aryl. R⁴ is selected from aryl, H,        R¹, alkyl, fluoroalkyl. In some embodiments R⁴ is aryl or        styryl. R⁷ is selected from aryl, heteroaryl, fluoroaryl,        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example up to 7 fluorine atoms and a crosslinkable group        attached to aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl        substituted with 1 or more fluorine atoms, for example up to 7        fluorine atoms.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (III) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, and acrosslinkable group. In further embodiments, substituents on twoneighboring aromatic rings in the compound of formula (III) can togetherform an aromatic or non-aromatic ring. In further embodiments, adjacentsubstituents on a single ring can be linked to form a fused aromatic ornon-aromatic ring.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, n=1, and R² is arylamino of formula(II), wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl.In some embodiments, n=1, R¹ is selected from phenyl, 1-naphthyl or2-naphthyl and R² is styryl or cinammate. In some embodiments, n=1, R¹is selected from phenyl, 1-naphthyl or 2-naphthyl and R² is arylamino offormula (II), wherein R⁴ is selected from aryl, H, styryl or cinnamate.In some embodiments, R⁴ is arylstyryl. In some embodiments, R¹ isselected from phenyl, 1-naphthyl or 2-naphthyl and R² is selected from Hor aryl and E is selected from (CR⁵R⁶)_(m), wherein R⁵ is selected fromalkyl, aryl, alkoxy and R⁶ is a crosslinkable group. In someembodiments, when R¹ or R³ are directly bound to a nitrogen atom, thecrosslinkable group is not a vinyl group.

In some embodiments, the device is selected from a light-emitting diode,a light-emitting diode display, a laser diode, a photodetector,photoconductive cell, photoresistor, photoswitch, phototransistor,phototube, IR-detector, photovoltaic device, solar cell, light sensor,photoconductor, electrophotographic device, transistor, and a diode.

Another aspect of the present invention is an electronic device havingat least one layer comprising a composition comprising a compound offormula

wherein:

-   -   R¹ is selected from aryl, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, and a crosslinkable group        attached to aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl        substituted with 1 or more fluorine atoms, for example, up to 7        fluorine atoms, and may be different at each occurrence (i.e.        copolymers). In some embodiments, R¹ is aryl. R² is selected        from H, aryl, alkyl, fluoroalkyl, Cl, Br, I, heteroaryl,        fluoroaryl, and fluoroheteroaryl substituted with 1 or more        fluorine atoms, for example, up to 7 fluorine atoms, a        crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms. In some embodiments, R² is H or        a crosslinkable group. R³ is selected from H and R¹. In some        embodiments, R³ is aryl. In some embodiments, R² is different        from R³. In some embodiments, R² is vinyl and R³ is aryl. R⁴ is        selected from aryl, H, R¹, alkyl, fluoroalkyl. In some        embodiments R⁴ is aryl. R⁷ is selected from aryl, heteroaryl,        fluoroaryl, fluoroheteroaryl substituted with 1 or more fluorine        atoms, for example up to 7 fluorine atoms and a crosslinkable        group attached to aryl, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example up to 7 fluorine atoms.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy and acrosslinkable group. In some embodiments, R¹ is selected from phenyl,1-naphthyl, and 2-naphthyl. In some embodiments, n=1, R² is H, and R³ isselected from phenyl, 1-naphthyl and 2-naphthyl, some embodiments, n=1,R¹ is selected from phenyl, 1-naphthyl and 2-naphthyl and R² is acinammyl group.

In some embodiments, the device is selected from a light-emitting diode,a light-emitting diode display, a laser diode, a photodetector,photoconductive cell, photoresistor, photoswitch, phototransistor,phototube, IR-detector, photovoltaic device, solar cell, light sensor,photoconductor, electrophotographic device, transistor, and a diode.

Another aspect of the present invention is an electronic device havingat least one layer comprising composition comprising copolymers preparedby copolymerizing at least one functional monomer having the formula (I)or (III) as defined hereinabove with at least one crosslinkable group asdefined above. The polymerization can be performed using thermal orphotochemical polymerization methods.

In some embodiments, the composition comprising a compound as disclosedherein is a liquid. The liquid can be in the form of, for example, asolution or dispersion.

A further aspect of the present invention is a process for making anelectronic device. The process includes: providing a liquid comprising acompound having the formula (I) as described hereinabove; providing ananode; contacting said liquid comprising said compound with said anode;Removing said liquid from said compound to produce a hole transportfilm; providing an emitter; disposing said emitter adjacent to said holetransport film; providing an electron transporter and disposing saidelectron transporter adjacent to said emitter; and providing a cathodeadjacent to said electron transporter. The liquid can be, for example, asolution or dispersion.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Unless otherwise defined, allletter symbols in the figures represent atoms with that atomicabbreviation. Although methods and materials similar or equivalent tothose described herein can be used in the practice or testing of thepresent invention, suitable methods and materials are described below.

All publications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety. Incase of conflict, the present specification, including definitions, willcontrol. In addition, the materials, methods, and examples areillustrative only and not intended to be limiting.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

DESCRIPTION OF THE DRAWINGS

The invention is illustrated by way of example and not limitation in theaccompanying figures.

FIG. 1: An illustrative example of one organic electronic devicecomprising at least one layer comprising a novel compound as disclosedherein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds disclosed herein are triarylamine derivatives, and can bein the form of dimers, oligomers or polymers, particularly dimers, andcontain crosslinkable groups. The compounds can provide the electronicadvantages of smaller molecules such as triarylamines, with the solutionprocessability, film forming capabilities, solubility properties, andthermal stability of polymeric compounds. In particular, it has beenfound that the compounds can be provided in solution and used insolution processes to manufacture electronic devices.

Also provided are compositions containing the compounds, includingliquid compositions.

In addition, the compounds can be rendered insoluble subsequent todeposition by thermal or photo-crosslinking reactions. Crosslinked filmsare generally more robust and resistant to solvents that may be used inlater processing steps. Crosslinking groups are well known, and any canbe used so long as they do not detrimentally affect the desiredproperties of the compounds in this invention.

In one embodiment, the electronic devices for which the compounds areuseful are OLED devices. In contrast to known compounds such as NPD(N,N′-di(naphthalen-1-yl)-N,N′-diphenyl-benzidine) and TPD(4,4′-bis[N-(3-methylphenyl)-N-phenylamino]biphenyl), which are commonlyused as hole transport materials in making electronic devices, generallyusing vapor deposition processes, the present compounds have improvedthermal stability and can be selectively solubilized in common solvents.By selectively solubilized is meant that the compounds can be made to besoluble or substantially soluble in some solvents and insoluble orsubstantially insoluble in other solvents. For example, in using thecompounds to make electronic devices it is often desirable to providethe compound in a solvent in which the compound is soluble orsubstantially soluble, and deposit thereon another solvent in which thecompound is insoluble or substantially insoluble. Solubilization can beprovided or enhanced by variation of substituent groups on thecompounds.

A suitable solvent for a particular compound or related class ofcompounds can be readily determined by one skilled in the art. For someapplications, it is desirable that the compounds be dissolved innon-aqueous solvents. Such non-aqueous solvents can be relatively polar,such as C1 to C20 alcohols, ethers, and acid esters, or can berelatively non-polar such as C1 to C12 alkanes or aromatics such astoluene, xylenes, trifluorotoluene and the like. Other suitable liquidsfor use in making a liquid composition, either as a solution ordispersion as described herein, comprising the new compounds, includes,but not limited to, chlorinated hydrocarbons (such as methylenechloride, chloroform, chlorobenzene), aromatic hydrocarbons (such assubstituted and non-substituted toluenes and xylenes), includingtriflurotoluene), polar solvents (such as tetrahydrofuran (THP),N-methyl pyrrolidone) esters (such as ethylacetate) alcohols(isopropanol), keytones (cyclopentatone) and mixtures thereof.

The present invention provides novel compounds, compositions and devicescontaining the compounds, and methods for making devices containing thecompounds. One aspect of the present invention is a compositioncomprising a compound having the formula:

wherein

-   -   n is an integer of at least 1 and R¹ is selected from aryl,        heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1        or more fluorine atoms, for example, up to 7 fluorine atoms, and        a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        and fluoroheteroaryl substituted with 1 or more fluorine atoms,        for example, up to 7 fluorine atoms. The compound comprises more        than one group R¹, and R¹ can be different at each occurrence.        For example, the compound represented by formula (I) can        function as a monomer, and copolymers can be formed from the        compound, such copolymers comprising, as polymerized units, a        plurality of units having formula (I) in which at least one unit        contains R¹ different from R¹ in other units. In some        embodiments, R¹ is aryl.

R³ is selected from H and R¹. R² is selected from H, aryl, alkyl,fluoroalkyl, Cl, Br, I, heteroaryl, fluoroaryl, and fluoroheteroarylsubstituted with 1 or more fluorine atoms, for example, up to 7 fluorineatoms, a crosslinkable group attached to aryl, heteroaryl, fluoroaryl,fluoroheteroaryl substituted with 1 or more fluorine atoms, for example,up to 7 fluorine atoms a crosslinkable group, and an arylamino group offormula (II),

R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl. In someembodiments R⁴ is aryl. R⁷ is selected from aryl, heteroaryl,fluoroaryl, and fluoroheteroaryl substituted with 1 or more fluorineatoms, for example, up to 7 fluorine atoms.

In some embodiments, R² is H. In some embodiments, R² is different fromR³. In some embodiments, R² is H and R³ is aryl.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) has one or more substituents independently selected from H,F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy,and fluoroaryloxy. In further embodiments, substituents on twoneighboring aromatic rings in the compound of formula (I) can togetherform an aromatic or non-aromatic ring. In further embodiments, adjacentsubstituents on a single ring can be linked to form a fused aromatic ornon-aromatic ring.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl. In some embodiments, n=1, R² is H, and R³ is selected fromphenyl, 1-naphthyl and 2-naphthyl.

Another aspect of the present invention is a composition comprising acompound of formula

wherein n is an integer of at least 1, R¹ is selected from aryl,heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1 or morefluorine atoms, for example, up to 7 fluorine atoms, and a crosslinkablegroup attached to aryl, heteroaryl, fluoroaryl, and fluoroheteroarylsubstituted with 1 or more fluorine atoms, for example, up to 7 fluorineatoms, and may be different at each occurrence (i.e. copolymers). R² isselected from H, aryl, alkyl, fluoroalkyl, Cl, Br, I, heteroaryl,fluoroaryl, and fluoroheteroaryl substituted with 1 or more fluorineatoms, for example, up to 7 fluorine atoms, a crosslinkable groupattached to aryl, heteroaryl, fluoroaryl, fluoroheteroaryl substitutedwith 1 or more fluorine atoms, for example, up to 7 fluorine atoms. acrosslinkable group, arylamino of formula (II).

wherein R⁴ is selected from aryl, H, R¹, alkyl, fluoroalkyl. In someembodiments R⁴ is aryl. R⁷ is selected from aryl, heteroaryl,fluoroaryl, fluoroheteroaryl substituted with 1 or more fluorine atoms,for example, up to 7 fluorine atoms, and a crosslinkable group attachedto aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1or more fluorine atoms, for example up to 7 fluorine atoms. In someembodiments, R² is H or aryl.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (III) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy. Infurther embodiments, substituents on two neighboring aromatic rings inthe compound of formula (III) can together form an aromatic ornon-aromatic ring. In further embodiments, adjacent substituents on asingle ring can be linked to form a fused aromatic or non-aromatic ring.

In some embodiments, R¹ is selected from phenyl, 1-naphthyl, 2-naphthyland styryl. In some embodiments, n=1, x=0, and R² is arylamino offormula (II), wherein R⁴ is selected from aryl, H, R¹, alkyl, andfluoroalkyl. In some embodiments, R⁴ is aryl.

Another aspect of the present invention is a composition comprising acompound of formula

wherein

-   -   R¹ is selected from aryl, heteroaryl, fluoroaryl, and        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, and a crosslinkable group        attached to aryl, heteroaryl, fluoroaryl, and fluoroheteroaryl        substituted with 1 or more fluorine atoms, for example, up to 7        fluorine atoms, and may be different at each occurrence (i.e.        copolymers). In some embodiments, R¹ is aryl. R² is selected        from H, aryl, alkyl, fluoroalkyl, Cl, Br, I, heteroaryl,        fluoroaryl, and fluoroheteroaryl substituted with 1 or more        fluorine atoms, for example, up to 7 fluorine atoms, a        crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        fluoroheteroaryl substituted with 1 or more fluorine atoms, for        example, up to 7 fluorine atoms, a crosslinkable group, Cl, Br,        I and an arylamino of formula (II).        wherein R⁴ is selected from aryl, H, R¹, alkyl, fluoroalkyl. In        some embodiments R⁴ is aryl. R⁷ is selected from aryl,        heteroaryl, fluoroaryl, fluoroheteroaryl substituted with 1 or        more fluorine atoms, for example, up to 7 fluorine atoms, and a        crosslinkable group attached to aryl, heteroaryl, fluoroaryl,        and fluoroheteroaryl substituted with 1 or more fluorine atoms,        for example up to 7 fluorine atoms. In some embodiments, R² is        different from R³. In some embodiments, R² is H and R³ is aryl.        In some embodiments, R² is H. R³ is selected from H and R¹. In        some embodiments, R³ is aryl.

E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of 1 to20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, and combinationsthereof, and can be different at each occurrence, wherein R⁵ and R⁶ areeach independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein R⁵ and R⁶ can, when taken together, form a non-aromatic ring,provided that when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1,at least one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.

In some embodiments, at least one aromatic ring in the compound offormula (I) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, and fluoroaryloxy. Insome embodiments, R¹ is selected from phenyl, 1-naphthyl, 2-naphthyl andstyryl. In some embodiments, n=1, R² is H, and R³ is selected fromphenyl, 1-naphthyl and 2-naphthyl.

The practical upper limit of n in formulas (I), (III) and (IV) isdetermined in part by the desired solubility of a compound in aparticular solvent or class of solvents. As the value of n increases,the molecular weight of the compound increases. The increase inmolecular weight is generally expected to result in a reduced solubilityof the compound in a particular solvent. Moreover, the value of n atwhich a compound becomes substantially insoluble in a given solvent isdependent in part upon the structure of the compound. For example, acompound containing multiple phenyl groups may become substantiallyinsoluble in an organic solvent when n is much less than about 10⁴. Asanother example, a compound containing fewer phenyl groups and/or phenylgroups with particular functional groups may be soluble in a givensolvent even though n is about 10⁴ or greater, even 10⁵ or 10⁶. Theselection of the value of n and a suitable solvent is within the purviewof one skilled in the art.

Also provided are compositions comprising novel copolymers prepared bycombining multiple functional monomers. The monomers are units ofcompounds disclosed herein, which can be polymerized to form the novelcopolymers. The monomers can be copolymerized, for example, using a Pdor Ni catalyzed polymerization procedure. Such monomers can be groupedinto three classes as follows:

Where y is an integer equal or greater than 1 and w is zero or aninteger equal or greater than one, and X is Cl, Br, I, boronic acid,boronic acid ester, boranes or a triflate group; ;and wherein X can bedifferent as each occurrence such that carbon-carbon (for Group 1) andcarbon-nitrogen bonds (for Groups 2 and 3) can be formed.

For convenience, exemplary monomers are assigned herein to Group 1,Group 2 or Group 3, and within the Groups, exemplary monomers areassigned to Subgroups such as, for example, within Group 1, subgroupsA1, A2, B, C1, C2, and C3.

Copolymers can be made using one or more monomers from each of subgroupswithin each of Group 1, Group 2, and/or Group 3, provided that nocopolymers containing only monomers from subgroups A or copolymerscontaining only monomers from subgroup B are obtained. Copolymers madefrom monomers within Group 3 contain at least one comonomer designatedA1 or A2, and at least one comonomer from subgroup E1, E2, E3, E4 andE5. Exemplary copolymers include poly(A-co-B); poly(A-co-C);poly(A-co-B-co-C); poly(A-co-C); and copolymers comprising two or moremonomers within group C, wherein, for example, “poly (A-co-B)” refers toa copolymer comprising, as polymerized units, monomers in Group A andmonomers in Group B. The monomers, e.g., A and B, in such copolymers,can be present in equimolar ratios or in non-equimolar ratios.Copolymers made from monomers in Group 1 are made by formation ofcarbon-carbon bonds during polymerization. Copolymers made from monomersin Groups 2 and Groups 3 are made by formation of carbon-nitrogen bondsduring polymerization.

The copolymers from Group 1 can generally be prepared using knownsynthetic methods. In one synthetic method, as described in Yamamoto,Progress in Polymer Science, Vol. 17, p 1153 (1992), the dihaloderivatives of the monomeric units are reacted with a stoichiometricamount of a zerovalent nickel compound, such asbis(1,5-cyclooctadiene)nickel(0). In another method, as described inColon et al., Journal of Polymer Science, Part A, Polymer chemistry,Edition, Vol. 28, p. 367 (1990), the dihalo derivatives of the monomericunits are reacted with catalytic amounts of Ni(II) compounds in thepresence of stoichiometric amounts of a material capable of reducing thedivalent nickel ion to zerovalent nickel. Suitable materials includezinc, magnesium, calcium and lithium. In the third synthetic method, asdescribed in U.S. Pat. No. 5,962,631, and published PCT application WO00/53565, a dihalo derivative of one monomeric unit is reacted with aderivative of another monomeric unit having two reactive groups selectedfrom boronic acid, boronic acid esters, and boranes, in the presence ofa zerovalent palladium catalyst, such as tetrakis(triphenylphosphine)Pd.

For example, homopolymers or copolymers containing monomers from Group 2can be formed by reacting a monomer unit having a reactive primary orsecondary amine and a reactive aryl halide in the presence of cupper,nickel or palladium catalysts. Homopolymers or copolymers containingmonomers from Group 3 can be produced by the reaction of one or moredihalo monomeric derivative(s) with one or more diamino (primary orsecondary) monomeric unit(s) in the presence of cupper, nickel orpalladium catalysts. Typical conditions for Pd-catalyzed aminationreactions are described in Sadighi, J. P.; Singer, R. A.; Buchwald, S.L. J. Am. Chem. Soc. 1998, 120, 4960; Wolfe, J. P.; Tomori, H.; Sadighi,J. P.; Yin, J.; Buchwald, S. L. J., Org. Chem. 200, 65, 1158; Hartwig,J. F.; Modern Arene Chemistry 2002, 107-168, Astruc, D., Editor,Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. Typical conditionsfor Ni-catalyzed amination reactions are described in Desmarets, C.;Schneider, R.; Fort, Y. Tetrahedron, 2001, 57, 6054.; Wolfe, J. P.;Buchwald, S. L., J. Am. Chem. Soc. 1997, 119, 4960. Typical conditionsfor Cu-catalyzed amination reactions are described in Klapars, A.;Antilla, J. C.; Huang, X.; Buchwald, S. L., J. Am. Chem. Soc. 2001, 123,7727.

Oligomers, including dimers, and polymers of the compounds disclosedherein have improved thermal stability in comparison to, e.g., NPD andTPD. For example, a compound of Formula IV wherein R¹ is 1-naphthyl andE is C(CF₃)₂ generally has a T_(g) of about 240° C. Typically, thecompounds have a T_(g) of at least about 50° C., generally at leastabout 100° C.

Compositions of formulas I and IV can be prepared via carbon-nitrogenbond formation methods known to one skilled in the art. For example,homo- or hetero-polymers can be produced by the reaction of one or moredihalo monomeric derivative(s) with equimolar amounts of one or morediamino (primary or secondary) monomeric unit(s) in the presence ofcopper, nickel or palladium catalysts. Alternatively, one or moremonomers containing an amine and a halide as reactive groups can beemployed. Typical conditions for Pd-catalyzed amination reactions aredescribed in Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem.Soc. 1998, 120, 4960.; Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin,J.; Buchwald, S. L. J. Org. Chem. 200, 65, 1158.; Hartwig, J. F. ModernArene Chemistry 2002, 107-168. Editor: Astruc, D., Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim, Germany. Typical conditions for Ni-catalyzedamination reactions are described in Desmarets, C.; Schneider, R.; Fort,Y. Tetrahedon, 2001, 57, 6054.; Wolfe, J. P.; Buchwald, S. L. J. Am.Chem. Soc. 1997, 119, 4960. Typical conditions for Cu-catalyzedamination reactions are described in Klapars, A.; Antilla, J. C.; Huang,X.; Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727.

For example, a diamine monomer E1 from Group 3, such asN,N′-diphenylbenzidine, is reacted with an equimolar amount of adihalide monomer A1, such as 4,4′-bromophenylisopropylidene, in presenceof a suitable base, such as NaO^(t)Bu, catalytic (less than oneequivalent) amount of a suitable palladium compound, such astris(dibenzylideneacetone) dipalladium, and a suitable ligand, such asP(tBu)₃. The polymerization is conducted at a temperature between 22° C.to 150° C. for 24 to 92 hours. The resulting polymer is then treatedwith an endcapping group, such as bromobenzene, and allowed to furtherreact for another 24 to 48 hours to produce a polymer of formula IV,where R¹ is phenyl, E is C(CH₃)₂ and R²═R³ is phenyl.

In another example, monomer D1 from Group 2, such as4-(N-phenylamine)-4′-(bromophenyl)isopropylidene, can be polymerizedusing conditions described above to give a polymer of formula IV, whereR¹ is phenyl, E is C(CH₃)₂ and R²═R³ is phenyl.

Compounds of formula III can be prepared via carbon-carbon bondformation methods known to one skilled in the art. In one method,described in Yamamoto, Progress in Polymer Science, Vol.17, p 1153(1992), the dihalo derivatives of the monomeric units are reacted with astoichiometric amount of a zerovalent nickel compound, such asbis(1,5-cyclooctadiene)nickel(0). In the second method, as described inColon et al., Journal of Polymer Science, Part A, Polymer chemistryEdition, Vol. 28, p. 367 (1990), the dihalo derivatives of the monomericunits are reacted with catalytic amounts of Ni(II) compounds in thepresence of stoichiometric amounts of a material capable of reducing thedivalent nickel ion to zerovalent nickel. Suitable materials includezinc, magnesium, calcium and lithium. In the third synthetic method, asdescribed in U.S. Pat. No. 5,962,631, and published PCT application WO00/53565, a dihalo derivative of one monomeric unit is reacted with aderivative of another monomeric unit having two reactive groups selectedfrom boronic acid, boronic acid esters, and boranes, in the presence ofa zerovalent palladium catalyst, such as tetrakis(triphenylphosphine)Pd.

For example, a polymeric composition of monomer C2 from Group 1, such as4,4′-N,N′-[(1-naphthyl)(4-chlorophenyl)]-(hexaflouroisopropylidene) isreacted with a stoichiometric amount of a zerovalent nickel compound,such as bis(1,5-cyclooctadiene)nickel(0), at a temperature between 22°C. to 150° C. for 24 to 92 hours.

For making electronic devices, including OLED devices, in someembodiments the compounds form films when deposited onto a transparentanode such as indium-doped tin oxide (ITO). The quality of the resultantfilm can be superficially judged by visual/microscopic inspection forsmoothness and defect density. In some embodiments that visuallyobserved defects be minimal. Furthermore, film quality can be measuredby estimation of film thickness over several separate areas of the filmusing, for example, an optical ellipsometer or a mechanicalprofilometer; In some embodiments that the films have substantiallyuniform thicknesses as measured in the different areas of the film.

The compounds can be used in liquid form, such as a dispersion orsolution, in making electronic devices. An exemplary process for makingan electronic device includes: providing a liquid comprising a compoundhaving the formula (I) as described hereinabove; providing an anode;contacting said liquid comprising said compound with said anode;Removing said liquid from said compound to produce a hole transportfilm; providing an emitter; disposing said emitter adjacent to said holetransport film; providing an electron transporter and disposing saidelectron transporter adjacent to said emitter; and providing a cathodeadjacent to said electron transporter.

The liquid is typically a solvent for the compound. For someapplications, the compounds can be dissolved in non-aqueous solvents.Such non-aqueous solvents can be relatively polar, such as C₁ to C₂₀alcohols, ethers, and acid esters, or can be relatively non-polar suchas C₁ to C₁₂ alkanes. As stated hereinabove, suitable solvents can bereadily selected by one skilled in the art.

In one embodiment, the compound is dissolved in a solvent in which thecompound is substantially soluble. The solution is then formed into athin film and dried by any of several known techniques such as spincoating, inkjetting etc. The resultant film formed as the solventevaporates is then further dried by baking at elevated temperaturesabove the boiling point of the solvent either in a vacuum of nitrogenatmosphere. The film is then subjected to further processing bydepositing a second solution containing emissive layer materials on topof the pre-formed compound film where the emissive materials aredissolved in a solvent in which the compound is substantially insoluble.By “substantially insoluble” is meant that less than about 5 mg of thecompound dissolves in 1 ml of the solvent. However, solubilities greaterthan or less than 5 mg can be used and may be desirable for someapplications. For example, a modest solubility up to 10 mg/mL may resultin a blurred or graded interface between the HTM polymer of the presentinvention and the emissive layer materials. Such blurring can havedeleterious or beneficial effects depending upon the natures of thematerials involved. Such blurring of the interface can result inimproved charge transport across the interface and substantiallyimproved device performance or lifetime.

As will be recognized by one skilled in the art, the solubility of acompound is determined in part by substituent groups within thecompound. In particular, in the compounds disclosed herein, the natureof the group “E” in the compound can be varied in order to control thesolubility of a compound in a particular solvent or class of solvents.Thus, by varying the nature of the group “E”, a compound can be modifiedsuch that is more or less soluble in water or any given organicnon-aqueous solvent.

Also, for making electronic devices, the compounds can have a relativelylow solubility, e.g., a solubility less than about 5 mg/mL, even about 2mg/mL or less, in solvents that can be used to deposit an emissive layerlayer film onto an electrode, which is typically a transparent anodesuch as ITO (indium doped tin oxide).

The present invention also relates to electronic devices comprising atleast one layer containing a composition as disclosed herein, as a holetransport layer. The compositions can be in a separate layer, positionedbetween a photoactive layer and an electrode. Alternatively, aphotoactive layer of an organic electronic device can contain thecomposition. An example of an electronic device that can contain acomposition as disclosed herein is shown in FIG. X. The device 100 hasan anode layer 110 and a cathode layer 160. Adjacent to the anode is alayer 120 comprising hole transport material. Adjacent to the cathode isa layer 140 comprising an electron transport and/or anti-quenchingmaterial. Between the hole transport layer and the electron transportand/or anti-quenching layer is the photoactive layer 130. In theillustrated embodiment, the device has an optional additional transportlayer 150, next to the cathode. Layers 120, 130, 140, and 150 areindividually and collectively referred to as the active layers.

Depending upon the application of the device 100, the photoactive layer130 can be a light-emitting layer that is activated by an appliedvoltage (such as in a light-emitting diode or light-emittingelectrochemical cell), a layer of material that responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector). Examples of photodetectors includephotoconductive cells, photoresistors, photoswitches, phototransistors,and phototubes, and photovoltaic cells, as these terms are describe inMarkus, John, Electronics and Nucleonics Dictionary, 470 and 476(McGraw-Hill, Inc. 1966).

The compounds disclosed herein are particularly useful in the holetransport layer 120, and as a charge conducting host in the photoactivelayer, 130. The other layers in the device can be made of any materialsthat are known to be useful in such layers. The anode, 110, is anelectrode that is particularly efficient for injecting positive chargecarriers. It can be made of, for example, materials containing a metal,mixed metal, alloy, metal oxide or mixed-metal oxide, a conductingpolymer, or a combination or mixture thereof. Suitable metals includethe Group 11 metals, the metals in Groups 4, 5, and 6, and the Group8-10 transition metals. If the anode is to be light-transmitting,mixed-metal oxides of Group 12, 13 and 14 metals, such asindium-tin-oxide, are generally used. The anode 110 can also comprise anorganic material such as polyaniline, as described, for example, in“Flexible light-emitting diodes made from soluble conducting polymer,”Nature vol. 357, pp 477-479 (11 Jun. 1992). In some embodiments, atleast one of the anode and cathode is at least partially transparent toallow the generated light to be observed.

Examples of the photoactive layer 130 include all knownelectroluminescent materials, including fluorescing and phosphorescingmaterials (including both organo-metallic complexes and conjugatedpolymers). Organometallic electroluminescent compounds are used in someembodiments, particularly cyclometalated iridium and platinumelectroluminescent compounds and mixtures thereof. Complexes of Iridiumwith phenylpyridine, phenylquinoline, or phenylpyrimidine ligands aredisclosed as electroluminescent compounds in Petrov et al., PublishedPCT Application WO 02/02714. Other organometallic complexes have beendescribed in, for example, published applications US 2001/0019782, EP1191612, WO 02/15645, and EP 1191614. Electroluminescent devices with anactive layer of polyvinyl carbazole (PVK) doped with metallic complexesof iridium have been described by Burrows and Thompson in published PCTapplications WO 00/70655 and WO 01/41512. Electroluminescent emissivelayers comprising a charge carrying host material and a phosphorescentplatinum complex have been described by Thompson et al., in U.S. Pat.No. 6,303,238, Bradley et al., in Synth. Met. (2001), 116 (1-3),379-383, and Campbell et al., in Phys. Rev. B, Vol.65 085210. Examplesof a few suitable iridium complexes are given in FIG. 6, as FormulaeIV(a) through IV(e). Analogous tetradentate platinum complexes can alsobe used. These electroluminescent complexes can be used alone, or dopedinto charge-carrying hosts, as noted above. The compounds, in additionto being useful in the hole transport layer 120, electronic transportlayer 140/150 can also act as a charge carrying host for an emissivedopant in the photoactive layer 130 or otherwise part of the photoactivelayer.

Examples of electron transport materials which can be used in layer 140and/or layer 150 include metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq₃); and azole compounds such as2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), andmixtures thereof.

The cathode 160, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layerand the cathode layer to lower the operating voltage.

It is known to have other layers in organic electronic devices. Forexample, there can be a layer (not shown) between the anode 110 and holetransport layer 120 to facilitate positive charge transport and/orband-gap matching of the layers, or to function as a protective layer.Layers that are known in the art can be used. In addition, any of theabove-described layers can be made of two or more layers. Alternatively,some or all of anode layer 110, the hole transport layer 120, theelectron transport layers 140 and 150, and cathode layer 160, may besurface treated to increase charge carrier transport efficiency. Thechoice of materials for each of the component layers can be made bybalancing the goals of providing a device with high device efficiencywith device operational lifetime.

It is understood that each functional layer may be made up of more thanone layer.

The devices can be prepared using a variety of techniques, includingsequentially vapor depositing the individual layers on a suitablesubstrate. Substrates such as glass and polymeric films can be used.Conventional vapor deposition techniques can be used, such as thermalevaporation, chemical vapor deposition, and the like. Alternatively, theorganic layers can be applied from solutions or dispersions in suitablesolvents, using any conventional coating or printing technique,including but not limited to spin-coating, dip-coating, roll-to-rolltechniques, ink-jet printing, screen-printing, gravure printing and thelike. Combinations of vapor deposition and solution coating ofindividual layers can be used. In general, the different layers have thefollowing range of thicknesses: anode 110, 500-5000 Å, frequently1000-2000 Å; hole transport layer 120, 50-2000 Å, frequently 200-1000 Å;photoactive layer 130, 10-2000 Å, frequently 100-1000 Å; electrontransport layer 140 and 150, 50-2000 Å, frequently 100-1000 Å; cathode160, 200-10000 Å, frequently 300-5000 Å. The location of theelectron-hole recombination zone in the device, and thus the emissionspectrum of the device, can be affected by the relative thickness ofeach layer. Thus the thickness of the electron-transport layer should bechosen so that the electron-hole recombination zone is in thelight-emitting layer. The desired ratio of layer thicknesses will dependon the exact nature of the materials used.

As used herein, unless expressly otherwise stated, the following termshave the meanings recited below.

The term “charge transport composition” is intended to mean materialthat can receive a charge from an electrode and facilitate its movementthrough the thickness of the material with relatively high efficiencyand small loss of charge. Hole transport compositions are capable ofreceiving a positive charge from an anode and transporting it. Electrontransport compositions are capable of receiving a negative charge from acathode and transporting it.

The term “composition”, used alone to refer to compositions havingparticular formulas disclosed and claimed herein, is intended to beconstrued broadly to include the compounds, monomers, dimers, oligomersand polymers thereof, as well as solutions, dispersions, liquid andsolid mixtures and admixtures.

The term “anti-quenching composition” is intended to mean a materialwhich prevents, retards, or diminishes both the transfer of energy andthe transfer of an electron to or from the excited state of thephotoactive layer to an adjacent layer.

The term “photoactive” refers to any material that exhibitselectroluminescence, photoluminescence, and/or photosensitivity.

The term “group” is intended to mean a part of a compound, such as asubstituent in an organic compound. The prefix “hetero” indicates thatone or more carbon atoms have been replaced with a different atom.

The term “alkyl” is intended to mean a group derived from an aliphatichydrocarbon having one point of attachment, which group may beunsubstituted or substituted. The term “heteroalkyl” is intended to meana group derived from an aliphatic hydrocarbon having at least oneheteroatom and having one point of attachment, which group may beunsubstituted or substituted.

The term “alkylene” is intended to mean a group derived from analiphatic hydrocarbon and having two or more points of attachment. Theterm “heteroalkylene” is intended to mean a group derived from analiphatic hydrocarbon having at least one heteroatom and having two ormore points of attachment.

The term “alkenyl” is intended to mean a group derived from ahydrocarbon having one or more carbon-carbon double bonds and having onepoint of attachment, which group may be unsubstituted or substituted.The term “alkynyl” is intended to mean a group derived from ahydrocarbon having one or more carbon-carbon triple bonds and having onepoint of attachment, which group may be unsubstituted or substituted.The term “alkenylene” is intended to mean a group derived from ahydrocarbon having one or more carbon-carbon double bonds and having twoor more points of attachment, which group may be unsubstituted orsubstituted. The term “alkynylene” is intended to mean a group derivedfrom a hydrocarbon having one or more carbon-carbon triple bonds andhaving two or more points of attachment, which group may beunsubstituted or substituted.

The terms “heteroalkenyl”, “heteroalkenylene”, ”heteroalkynyl” and“heteroalkynylene” are intended to mean analogous groups having one ormore heteroatoms.

The term “aryl” is intended to mean a group derived from an aromatichydrocarbon having one point of attachment, which group may beunsubstituted or substituted. The term “heteroaryl” is intended to meana group derived from an aromatic group having at least one heteroatomand having one point of attachment, which group may be unsubstituted orsubstituted.

Unless otherwise indicated, all groups can be unsubstituted orsubstituted. The phrase “adjacent to,” when used to refer to layers in adevice, does not necessarily mean that one layer is immediately next toanother layer. On the other hand, the phrase “adjacent R groups,” isused to refer to R groups that are next to each other in a chemicalformula (i.e., R groups that are on atoms joined by a bond). The term“vicinal” means on adjoining atoms in a ring or chain.

The term “compound” is intended to mean an electrically unchargedsubstance made up of molecules that further consist of atoms, whereinthe atoms cannot be separated by physical means.

The term “polymeric” is intended to encompass oligomeric species andinclude materials having 2 or more monomeric units. In addition, theIUPAC numbering system is used throughout, where the groups from thePeriodic Table are numbered from left to right as 1 through 18 (CRCHandbook of Chemistry and Physics, 81st Edition, 2000).

As used herein, “solution processing” means processes that includedepositing from a liquid medium. The liquid medium can be in the form ofa solution, a dispersion, an emulsion, or other forms.

The term “film” refers to a coating covering a desired area. The areacan be as large as an entire display, or as small as a single sub-pixel.Films can be formed by any conventional deposition technique. Typicaldeposition techniques include, but are not limited to, continuousdeposition techniques such as spin coating, gravure coating, curtaincoating, dip coating, slot-die coating, spray-coating, and continuousnozzle coating; and discontinuous deposition techniques such as ink jetprinting, gravure printing, and screen printing.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, “the”, “a” or “an” are employed to describe elements andcomponents of the invention. This is done merely for convenience and togive a general sense of the invention. This description should be readto include one or at least one and the singular also includes the pluralunless it is obvious that it is meant otherwise.

EXAMPLES

The following examples illustrate certain features and advantages of thepresent invention. They are intended to be illustrative of theinvention, but not limiting. All percentages are by weight, unlessotherwise indicated.

Example 1

This example illustrates the preparation of one exemplary compound:

Synthesis of Vinyl Iodoacetate

A 100 mL round bottom flask equipped with a mechanical stirrer andnitrogen inlet-outlet was charged with vinyl chloroacetate (3.83 g, 31.8mmol) in 50 mLs acetone. Sodium iodide (39.4 mmol) was added resultingin a moderate temperature rise upon initiation of the reaction. Thereaction was stirred at room temperature for two days and thenconcentrated on a rotary evaporator. The residue was dissolved in 100 mLdiethyl ether and washed two times with 100 mL water, once with 10 wt %aq. sodium bisulfite (aq.), once with 100 mL water and once with 100 mLsaturated aq. NaCl. The organic layer was dried over MgSO₄, filtered andconcentrated on a rotary evaporator. The residue was furtherconcentrated on a high vacuum line to give 5.6 g product as a light pinkoil. The yield was 82%.

Synthesis of Vinyl-4-(N,N-diphenylamino)cinnamate

A 100 mL round bottom flask equipped with a nitrogen inlet-outlet,magnetic stirrer and addition funnel was charged with vinyl iodoacetate(5.6 g, 26 mmol) and triphenylphosphine (6.9 g, 26 mmol) in 50 mLanhydrous tetrahydrofuran. The reaction mixture was blanketed withnitrogen and allowed to stir for 16 h and then cooled to 6° C. on anice-water bath. Sodium hydride (1.0 g, 25 mmol) was added and thereaction was allowed to warm to room temperature. After stirring at roomtemperature for 4 h, 4-diphenylaminobenzaldehyde (5.4 g, 20 mmol)dissolved in 40 mL anhydrous THF was added dropwise to the stirringreaction mixture over 30 minutes. After stirring at room temperature forfive days, the reaction mixture was diluted with 50 mL diethyl ether andtransferred to a separatory funnel. An additional 300 mL diethyl etherwas added to the separatory funnel and the combined ether solution waswashed three times with 100 mL water and one time with 100 mL saturatedNaCl solution. The organic layer was dried over MgSO₄, filtered andconcentrated on a rotary evaporator. The residue was further dried on ahigh vacuum line to yield the crude product as a brown oil. Afterpurification by flash column chromatography (silica gel; 3:7dichloromethane:hexanes) 5.5 g of the pure product was obtained as alight yellow oil. The product yield was 81%.

Synthesis of poly[Vinyl-4-(N,N-diphenylamino)cinnamate]

A clean, dry 25 mL Schlenk tube was equipped with a magnetic stir barand a septum seal and then charged withvinyl-4-(N,N-diphenylamino)cinnamate (0.86 g, 2.5 mmol), Vazo 52 (5 mg,0.8 mol %) and tetrahydrofuran (0.86 g). The Schlenk tube was sealed anddegassed with three freeze-pump-thaw cycles under nitrogen and thensealed. The contents were heated in a thermostatted oil bath set to 57°C. for 48 h. After this time, the polymerization was allowed to cool andthen diluted with 3 mL tetrahydrofuran. The polymer was isolated byprecipitation from 80 mL stirring hexanes. The polymer was furtherpurified by flash column chromatography (neutral alumina; 1:1hexanes:dichloromethane). After removal of solvent, 220 mg of a yellowsolid was obtained. The yield was 25.5%. The polymer obtained in thisway was free of monomer. The molecular weight of the polymer wasdetermined by gel permeation chromatography. M_(w)=280,900;M_(n)=52,300; M_(w)/M_(n)=5.37.

Example 2

Synthesis of 4-(N,N-diphenylamino)cinnamic acid

All glassware was dried in a drying oven heated to 140° C. Malonic acidwas dried on a high vacuum line over P₂O₅ and then stored in a nitrogenpurged glovebox. Pyridine (Aldrich, anhydrous, 99.8 %) and piperidinewere used as received and stored in the glovebox. In a 100 mL roundbottom flask equipped with a stir bar, condenser and nitrogeninlet-outlet was dissolved malonic acid (2.3 g, 22.0 mmol) in 20 mLpyridine. 4-(N,N-Diphenylamino)benzaldehyde (5.0 g, 18.3 mmol) was addedand addition of 20 mL pyridine was necessary to obtain a solution.Piperidine (0.18 mL, 1.8 mmol) was added and the solution was heated toreflux. After heating for 25 hours, malonic acid (0.60 g, 5.8 mmol) wasadded and heating was resumed for an additional 2.5 h after which timeno further reaction was observed. The reaction mixture was allowed tocool to room temperature and then poured into a stirring mixture of 12 NHCl in ice water (1:5). The mixture was filtered and the solids rinsedthree times with 20 mL water. The solids were collected and the crudeproduct was purified by recrystallization from 5:3 hexanes:EtOAc at 4°C. The mother liquor was concentrated and recrystallized in a similarfashion from 7:3 hexanes:ethyl acetate. The combined crops give 3.1 g ofa light brown powder. The yield was 55%.

Synthesis of 4-(N,N-diphenylamino)cinnamoyl chloride

A 50 mL round bottom flask equipped with a magnetic stirrer and anitrogen inlet-outlet was charged with 4-(N,N-diphenylamino)cinnamicacid (1.0 g, 3.2 mmol) in 15 mL dichloromethane. Thionyl chloride (0.35mL, 4.8 mmol) was added followed by 12.4 □L N,N-dimethylformamide.Hydrogen chloride gas evolution began immediately and then ceased withinone hour of stirring. The solution was stirred for 3 h and thenconcentrated on a rotary evaporator. The product was transferred to ahigh vacuum line and residual solvent was removed under vacuum. Theproduct was obtained as a brown solid and stored under nitrogen withoutany further purification.

1. A compound having the formula:

wherein n is an integer of at least 1 and R¹ is selected from aryl,heteroaryl, fluoroaryl substituted with 1 or more fluorine atoms,fluoroheteroaryl substituted with 1 or more fluorine atoms, and acrosslinkable group attached to aryl, heteroaryl, fluoroaryl, orfluoroheteroaryl substituted with 1 or more fluorine atoms; R³ isselected from H and R¹; R² is selected from H, aryl, alkyl, fluoroalkyl,Cl, Br, I, heteroaryl, fluoroaryl substituted with 1 or more fluorineatoms, fluoroheteroaryl substituted with 1 or more fluorine atoms; acrosslinkable group attached to aryl, heteroaryl, fluoroaryl substitutedwith 1 or more fluorine atoms or fluoroheteroaryl substituted with 1 ormore fluorine atoms, a crosslinkable group, and an arylamino group offormula (II),

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl; R⁷ isselected from aryl, heteroaryl, fluoroaryl substituted with 1 or morefluorine atoms, fluoroheteroaryl substituted with 1 or more fluorineatoms, and a crosslinkable group attached to aryl, heteroaryl,fluoroaryl substituted with 1 or more fluorine atoms or fluoroheteroarylsubstituted with 1 or more fluorine atoms; E is selected from O, S,(SiR⁵R⁶)_(m) wherein m is an integer of 1 to 20, (CR⁵R⁶)_(m) wherein mis an integer of 1 to 20, and combinations thereof, wherein R⁵ and R⁶are each independently selected from H, F, alkyl, aryl, alkoxy, aryloxy,fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, a crosslinkablegroup, and a crosslinkable group attached to alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fouoroaryl, fluoroalkoxy, or fluoroaryloxy, andwherein when E is (CR⁵R⁶)_(m), and n is greater than 1 and m is 1, atleast one of R⁵ and R⁶ is not hydrogen or a hydrocarbon.
 2. The compoundof claim 1, wherein at least one aromatic ring in the compound offormula (I) has one or more substituents independently selected from H,F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy,fluoroaryloxy, and crosslinkable groups.
 3. The compound of claim 1,wherein R⁵ and R⁶, when taken together, form a non-aromatic ring.
 4. Thecompound of claim 1, wherein two or more substituents on two neighboringaromatic rings in the compound of formula (I) together form an aromaticor non-aromatic ring.
 5. The compound of claim 1, wherein adjacentsubstituents on a single ring are linked to form a fused aromatic ornon-aromatic ring.
 6. The compound of claim 1, wherein R¹ is selectedfrom phenyl, 1-naphthyl, and 2-naphthyl, cinnamate and chalcone groups.7. The compound of claim 1, wherein n=1, R² is H, and R³ is selectedfrom phenyl, 1-naphthyl, 2-naphthyl and styryl.
 8. A compound of formula

wherein n is an integer of at least 1, R¹ is selected from aryl,heteroaryl, fluoroaryl, and fluoroheteroaryl substituted with 1 or morefluorine atoms, and a crosslinkable group attached to aryl, heteroaryl,fluoroaryl, and fluoroheteroaryl substituted with 1 or more fluorineatoms, R² is selected from H, aryl, alkyl, fluoroalkyl, Cl, Br, I,heteroaryl, fluoroaryl substituted with 1 or more fluorine atoms,fluoroheteroaryl substituted with 1 or more fluorine atoms, acrosslinkable group attached to aryl, heteroaryl, fluoroaryl substitutedwith 1 or more fluorine atoms or fluoroheteroaryl substituted with 1 ormore fluorine atoms, a crosslinkable group, and arylamino of formula(II)

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl; R⁷ isselected from aryl, heteroaryl, fluoroaryl substituted with 1 or morefluorine atoms, fluoroheteroaryl substituted with 1 or more fluorineatoms, and a crosslinkable group attached to aryl, heteroaryl,fluoroaryl, and fluoroheteroaryl substituted with 1 or more fluorineatoms; E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of1 to 20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, andcombinations thereof, wherein R⁵ and R⁶ are each independently selectedfrom H, F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl,fluoroalkoxy, fluoroaryloxy, a crosslinkable group, and a crosslinkablegroup attached to alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fouoroaryl,fluoroalkoxy, or fluoroaryloxy, provided that when E is (CR⁵R⁶)_(m), andn is greater than 1 and m is 1, at least one of R⁵ and R⁶ is nothydrogen or a hydrocarbon.
 9. The compound of claim 8, wherein R⁵ andR⁶, when taken together, form a non-aromatic ring,
 10. The compound ofclaim 8, wherein at least one aromatic ring in the compound of formula(III) has a substituent selected from H, F, alkyl, aryl, alkoxy,aryloxy, fluoroalkyl, fluoroaryl, fluoroalkoxy, fluoroaryloxy, and acrosslinkable group.
 11. The compound of claim 8, wherein two or moresubstituents on two neighboring aromatic rings in the compound offormula (III) together form an aromatic or non-aromatic ring.
 12. Thecompound of claim 8, wherein adjacent substituents on a single ring arelinked to form a fused aromatic or non-aromatic ring.
 13. The compoundof claim 8 wherein R¹ is selected from phenyl, 1-naphthyl, and2-naphthyl.
 14. The compound of claim 8, wherein n=1, and R² isarylamino of formula (II), wherein R⁴ is selected from aryl, H, R¹,alkyl, and fluoroalkyl.
 15. The compound of claim 8 wherein n=1, R¹ isselected from phenyl, 1-naphthyl or 2-naphthyl and R² is styryl orcinammate, or arylamino of formula (II), wherein R⁴ is selected fromaryl, H, styryl and cinnamate.
 16. The compound of claim 8 wherein R¹ isselected from phenyl, 1-naphthyl and 2-naphthyl and R² is selected fromH and aryl and E is selected from (CR⁵R⁶)_(m), wherein R⁵ is selectedfrom alkyl, aryl, and alkoxy and R⁶ is a crosslinkable group.
 17. Acompound of formula

wherein: R¹ is selected from aryl, heteroaryl, fluoroaryl, andfluoroheteroaryl substituted with 1 or more fluorine atoms, and acrosslinkable group attached to aryl, heteroaryl, fluoroaryl, andfluoroheteroaryl substituted with 1 or more fluorine atoms; R² isselected from H, aryl, alkyl, fluoroalkyl, Cl, Br, I, heteroaryl,fluoroaryl, and fluoroheteroaryl substituted with 1 or more fluorineatoms, a crosslinkable group attached to aryl, heteroaryl, fluoroarylsubstituted with 1 or more fluorine atoms, fluoroheteroaryl substitutedwith 1 or more fluorine atoms, a crosslinkable group, and an arylaminogroup of formula (II),

wherein R⁴ is selected from aryl, H, R¹, alkyl, and fluoroalkyl; R⁷ isselected from aryl, heteroaryl, fluoroaryl substituted with 1 or morefluorine atoms, fluoroheteroaryl substituted with 1 or more fluorineatoms, and a crosslinkable group attached to aryl, heteroaryl,fluoroaryl, and fluoroheteroaryl substituted with 1 or more fluorineatoms; E is selected from O, S, (SiR⁵R⁶)_(m) wherein m is an integer of1 to 20, (CR⁵R⁶)_(m) wherein m is an integer of 1 to 20, andcombinations thereof, wherein R⁵ and R⁶ are each independently selectedfrom H, F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl,fluoroalkoxy, fluoroaryloxy, a crosslinkable group, and a crosslinkablegroup attached to alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fouoroaryl,fluoroalkoxy, or fluoroaryloxy, provided that when E is (CR⁵R⁶)_(m), andn is greater than 1 and m is 1, at least one of R⁵ and R⁶ is nothydrogen or a hydrocarbon.
 18. The compound of claim 17 wherein at leastone aromatic ring in the compound of formula (I) has a substituentselected from H, F, alkyl, aryl, alkoxy, aryloxy, fluoroalkyl,fluoroaryl, fluoroalkoxy, fluoroaryloxy and a crosslinkable group. 19.The compound of claim 17 wherein R¹ is selected from phenyl, 1-naphthyl,and 2-naphthyl.
 20. The compound of claim 17 wherein n=1, R² is H, andR3 is selected from phenyl, 1-naphthyl, 2-naphthyl and styryl. In someembodiments, n=1, R¹ is selected from phenyl, 1-naphthyl and 2-naphthyland R² is styryl or cinammate.
 21. The compound of claim 17 wherein R⁵and R⁶, taken together, form a non-aromatic ring.
 22. A compoundcomprising a copolymers prepared by copolymerizing at least one compoundof claim 1 and at least one compound of claim 8, said compound of claim1 or claim 8 comprising at least one crosslinkable group.
 23. Acomposition comprising a compound of claim
 1. 24. A compositioncomprising a compound of claim
 8. 25. A composition comprising acompound of claim
 17. 26. An electronic device having at least one layercomprising a composition of claim
 1. 27. An electronic device having atleast one layer comprising a composition of claim
 8. 28. An electronicdevice having at least one layer comprising a composition of claim 17.29. The device of claim 26, wherein the layer is a charge transportlayer.
 30. The device of claim 26, wherein the layer is a light-emittinglayer.
 31. The device of claim 27, wherein the layer is a chargetransport layer.
 32. The device of claim 27, wherein the layer is alight-emitting layer.
 33. The device of claim 28, wherein the layer is acharge transport layer.
 34. The device of claim 28, wherein the layer isa light-emitting layer.
 35. The device of claim 26, wherein the deviceis selected from a light-emitting diode, a light-emitting diode display,a laser diode, a photodetector, photoconductive cell, photoresistor,photoswitch, phototransistor, phototube, IR-detector, photovoltaicdevice, solar cell, light sensor, photoconductor, electrophotographicdevice, transistor, or diode.
 36. The device of claim 27, wherein thedevice is selected from a light-emitting diode, a light-emitting diodedisplay, a laser diode, a photodetector, photoconductive cell,photoresistor, photoswitch, phototransistor, phototube, IR-detector,photovoltaic device, solar cell, light sensor, photoconductor,electrophotographic device, transistor, or diode.
 37. The device ofclaim 28, wherein the device is selected from a light-emitting diode, alight-emitting diode display, a laser diode, a photodetector,photoconductive cell, photoresistor, photoswitch, phototransistor,phototube, IR-detector, photovoltaic device, solar cell, light sensor,photoconductor, electrophotographic device, transistor, or diode.